52nd Lunar and Planetary Science Conference 2021 (LPI Contrib. No. 2548) 2266.pdf

COMBINED MEASUREMENTS BY LASER INDUCED BREAKDOWN SPECTROSCOPY AND LASER ABLATION MOLECULAR ISOTOPIC SPECTROMETRY FOR PLANETARY EXPLORATION. E. A. Lalla1, M. G. Daly1, A. Quaglia2, S. Walker2, G. Flynn2, G. Levy2, and M. Konstantinidis1. 1Department of Earth & Space Science & Engineering, Lassonde School of Engineering, York University, Toronto, Ontario, Canada, ([email protected]). 2Sciencetech Inc, 1450 Global Drive, London, Ontario, Canada. 3Dalla Lana School of Public Health, University of Toronto, 155 College St. Toronto, Canada.

Introduction: The Canadian Space Agency (CSA) LIBS and LAMIS for Planetary is providing financial support, as part of the effort from Exploration: LIBS and LAMIS are two techniques that the Government of Canada, to Canadian Companies to could be combined in a concept instrument for space for increasing their competitiveness in space exploration and further improve the capabilities of technologies [1] future space missions (i.e., to Mars or the Moon). The STPD Program from the CSA supports basic Moreover, the proposed system will benefit from both research and development (R&D) in new space techniques and hence have the capability of elemental technologies that encourage innovation and increase composition analysis, isotopic measurements without Canadian industrial capabilities [1]. These efforts are sample preparation, rapid surface mapping and depth paramount to increase the role of the Canadian Space profiling [5]. industry as key collaborators in planetary missions and Laser ABlation Elemental ISotopic Spectrometer further industrial applications. (LABEISS): This project is being undertaken and lead Laser Induced Breakdown Spectroscopy by Sciencetech Inc. (SCI) and the Planetary Exploration (LIBS): The progress and development of new portable Instrumentation Laboratory (PIL) at York University. analytical techniques for planetary exploration have The LABEISS project is focused on providing new facilitated the development of autonomous planetary insight into a putative instrument that combines the rovers by various Space agencies such as NASA, ESA, LIBS and LAMIS technologies mentioned above. and CNSA. Laser-Induced breakdown spectroscopy Moreover, the project is aligned to provide Basic R&D (LIBS) has become one of the most efficient and reliable of space technology to be used in future missions while techniques onboard different rovers such as ChemCam exploring extraterrestrial environments. It will provide and the most recently evolved system – SuperCam isotopic analyses with a precision that can help our onboard on NASA Mars2020 Perseverance [2, 3]. understanding of how these bodies came to be, their Indeed, LIBS is a rapid methodology for obtaining continuing dynamics, and even give clues to analytical results of major and minor elements in biologically related processes. The current status of the geological samples, soil samples, and surface cleaning LABEISS system is being undertaken via two parallel (with repetitive laser ablation). Furthermore, LIBS can and interrelated tasks: “Science” and “Engineering.” obtain quantitative and qualitative information on the The primary challenge (Science) of LABEISS is to sample’s composition for different planetary surfaces. determine the best implementation by which to combine Also, the LIBS technique is aligned with CSA research the LAMIS method with LIBS to determine isotopic priorities for future planetary exploration that includes: elemental composition and quantification for different Planetary Science, Astrobiology, Planetary Geology, targets. This challenge includes scientific research and Geophysics and Prospecting, Planetary Space characterization of the selected targets of planetary Environment, and Space Health [4]. interest (space simulant, meteorites and certified Laser Ablation Molecular Isotopic Spectrometry isotopic samples) such as: 1) understanding of the (LAMIS): LIBS, like many other methods (e.g., Raman relationship between line intensity in the spectrum and Spectroscopy or X-Ray Diffraction) present some the concerned isotopic mass fractions in the samples; 2) limitation in their ability to characterize the geological research of the electronically, vibrationally and origin of a sample and several features can be lost (e.g., rotationally excited “isotopologues” of dimers, oxides, geochronology, isotopic features and possible origin of nitrides or halides in plasma reactions of the ablated organic matter). To address these limitations, LAMIS sample atomized matter. has emerged as a promising complementary technique The second engineering challenge of the proposal to cover some of the limitations of LIBS. LAMIS is includes developing a robust system that can be applied based on isotopic shift (so-called isotopologues) from in future planetary space exploration and other fields the molecular emission at a time delay defined in terms such as geology and archeology, among other emerging of when the plasma and atoms associate during the laser needs of the marketplace. Our engineering and design ablation [5]. approach starts with a baseline Instrument. We are determining and selecting the spectroscopic 52nd Lunar and Planetary Science Conference 2021 (LPI Contrib. No. 2548) 2266.pdf

(Spectrometer + gated camera) system, laser system, augmentation will consist of a X-Y LIBS-LAMIS and optics, according to the technical and scientific scanning mode. Furthermore, scanning capability would requirements of LIBS and LAMIS. be particularly advantageous with 3D-mobile stages for Subsequently, we plan to set up the LABEISS mapping which would result in high-fidelity (to real breadboard with the selected mechanical and optical missions) result. The second augmentation intended is configuration (Laser, Spectrometer, camera, optical to create a vacuum simulation chamber, as shown in configuration and sensing distances). Finally, we will Figure 1. Using a simulation chamber, we aim to characterize the breadboard with respect to key demonstrate the performance of LIBS-LAMIS in a characteristics such as required laser power, sensing laboratory and different planetary environments such as distance, spectrometer configuration (delay time, Earth, Moon and Mars. acquisition time, delay-width), and calibration methods Spectrometer Design: The state of the art in LIBS (intensity and wavelengths). As such, the full and LAMIS spectroscopies involves designing a characterization will help us establish the definition of specific spectrometer with a suitable resolution and single measurements vs tandem measurements (e.g. capabilities to carry out LAMIS and LIBS SNR versus number of shots), the limit of detection measurements. Therefore, we are performing (LOD) and the limit of identification (LOI) in LIBS and experiments to understand the required resolution and LAMIS. signal-to-noise ratio to perform both LIBS and LAMIS LABEISS breadboard configuration: The measurements sequentially (or in parallel). These proposed configuration for the LABEISS Breadboard is measurements will enable us to prototype the most shown in Figure 1. It will employ a 1064 nm pulsed laser suitable spectrometer for LIBS and LAMIS and be (the output power, pulse duration and frequency TBD). finally integrated into the LABEISS breadboard. The incoming beam will be delivered through fibre Summary, current status and future optics and expanded by using a variable beam expander. activities: Our Phase 0 study, until April 2021, is Subsequently, the ablation scattering will be focused building the prototype the system for LAMIS. onto the sample with an off-axis parabolic mirror coated Subsequently we will determine the parameters and for 1064 nm. The backscattered radiation from LIBS spectrometer requirements for a custom LAMIS and LAMIS will be collected using the LIBS-LAMIS instrument. These results will be used to roadmap a probe head and subsequently delivered to the future instrument development and possible flight on a spectrometer with optic fibres, as shown in Figure 1. planetary mission in the near future. At this conference, we will report on the latest results of the current project. Acknowledgments: We acknowledge the support of the Canadian Space Agency. This study is partially supported with funding from Sciencetech Inc and York University. M. G. Daly is thankful for the financial support provided by the Natural Sciences and Engineering Research Council of Canada (NSERC) References:[1] https://www.asc-csa.gc.ca/eng /funding-programs/funding-opportunities/ao/2019- stdp-ao-6-1.asp. [2] Weins R. C. et al. (2013) Spectrochim. Acta Part B 82: 1–27. [3] Weins R. C. et al. (2021) Space Sci Rev: 217 (1): 4. [4] https://www.asc-csa.gc.ca/eng/publications/rpp- 2016.asp. [5] Bol’shakov et al. (2016) J. Anal. At. Spectrom 31, 119-134. Figure 1. Sketched configuration of the LABEISS

breadboard system.

To fulfill the scientific requirements and establish a better approach to emulate real, in-situ measurements under laboratory conditions, we will include several augmentations. We are thereby addressing the scientific and technical limitations of the LABEISS breadboard in advance, which will increase the chances of developing a successful future flight instrument. The first